EP3342824B1 - Composition de résine de polycarbonate et son article moulé - Google Patents

Composition de résine de polycarbonate et son article moulé Download PDF

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Publication number
EP3342824B1
EP3342824B1 EP16839386.6A EP16839386A EP3342824B1 EP 3342824 B1 EP3342824 B1 EP 3342824B1 EP 16839386 A EP16839386 A EP 16839386A EP 3342824 B1 EP3342824 B1 EP 3342824B1
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Prior art keywords
polycarbonate
based resin
resin composition
group
carbon atoms
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German (de)
English (en)
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EP3342824A1 (fr
EP3342824A9 (fr
EP3342824A4 (fr
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Tomoko Abe
Yasuhiro Ishikawa
Makoto Ando
Hiroshi Yamaguchi
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/10—Polysulfonamides; Polysulfonimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the present invention relates to a polycarbonate-based resin composition containing a polycarbonate-polyorganosiloxane copolymer and a molded article thereof.
  • PC-POS copolymer A polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as "PC-POS copolymer”) has been attracting attention because of its excellent properties, such as high impact resistance, chemical resistance, and flame retardancy. Accordingly, the polycarbonate-polyorganosiloxane copolymer has been expected to be widely utilized in various fields, such as the field of electrical and electronic equipment and the field of automobiles. In particular, the utilization of the polycarbonate-polyorganosiloxane copolymer in casings for a cellular phone, a mobile personal computer, a digital camera, a video camera, an electric tool, and the like, and in other commodities has been expanding.
  • a homopolycarbonate using 2,2-bis(4-hydroxyphenyl)propane [common name: bisphenol A] as a dihydric phenol serving as a raw material has been generally used as a typical polycarbonate.
  • a polycarbonate-polyorganosiloxane copolymer using a polyorganosiloxane as a copolymerizable monomer has been known for improving the physical properties of the homopolycarbonate, such as flame retardancy and impact resistance (Patent Document 1).
  • Examples of an approach to further improving the impact resistance of a polycarbonate resin containing the polycarbonate-polyorganosiloxane copolymer may include an approach involving using a polyorganosiloxane having a long chain length, and an approach involving increasing the amount of the polyorganosiloxane in the polycarbonate-polyorganosiloxane copolymer as described in Patent Documents 2 and 3.
  • Patent Document 4 discloses compositions comprising polycarbonate and polycarbonate-polysiloxane copolymer in which the polysiloxane blocks form domains of a certain size in the PC-matrix.
  • An object of the present invention is to provide a polycarbonate-based resin composition containing a polycarbonate-polyorganosiloxane copolymer having impact resistance more excellent than that of a known polycarbonate-based resin.
  • the inventors of the present invention have found that when a polycarbonate-based resin composition containing a polycarbonate-polyorganosiloxane copolymer having a specific structure is used, impact resistance more excellent than that of a polycarbonate-based resin composition having a comparable polyorganosiloxane chain length or containing a comparable polyorganosiloxane block amount is obtained.
  • the present invention relates to the following items [1] to [21].
  • the polycarbonate-based resin composition containing the polycarbonate-polyorganosiloxane copolymer has a specific structure, and hence a polycarbonate-based resin composition excellent in impact resistance, in particular, low-temperature impact resistance, and a molded article thereof can be obtained.
  • the inventors of the present invention have made extensive investigations, and as a result, have found that when a polycarbonate-based resin composition containing a polycarbonate-polyorganosiloxane copolymer having a specific structure is used, low-temperature impact resistance more excellent than that of a polycarbonate-based resin composition having a comparable polyorganosiloxane chain length or containing a comparable polyorganosiloxane block amount is obtained.
  • a polycarbonate-based resin composition containing a polycarbonate-polyorganosiloxane copolymer having a specific structure is used, low-temperature impact resistance more excellent than that of a polycarbonate-based resin composition having a comparable polyorganosiloxane chain length or containing a comparable polyorganosiloxane block amount is obtained.
  • Detailed description is given below.
  • a polycarbonate-based resin composition of the present invention contains a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) comprising a repeating unit represented by the following general formula (II), and an aromatic polycarbonate-based resin (B) except the polycarbonate-polyorganosiloxane copolymer (A), and has a structure in which a domain (d-1) containing the polyorganosiloxane block (A-2) is present in a matrix containing the aromatic polycarbonate-based resin (B) as a main component, and a domain (d-2) containing at least one selected from a block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1) is present inside the domain (d-1):
  • R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms
  • X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 -, -O- or -CO-, and a and beach independently represent an integer of from 0 to 4; and in the general formula (II), R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1
  • the content of the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate-based resin composition of the present invention is typically from 0.1 mass% to 99.9 mass%, preferably from 1 mass% to 99 mass%, more preferably from 2 mass% to 50 mass%, still more preferably from 5 mass% to 20 mass% from the viewpoints of the ease with which the resin composition is produced and the impact resistance of the resin composition to be obtained.
  • the content of the aromatic polycarbonate-based resin (B) in the polycarbonate-based resin composition of the present invention is typically from 99.9 mass% to 0.1 mass%, preferably from 99 mass% to 1 mass%, more preferably from 98 mass% to 50 mass%, still more preferably from 95 mass% to 80 mass% from the viewpoints of the ease with which the resin composition is produced and the impact resistance of the resin composition to be obtained.
  • a mass ratio "(A)/(B)" of the polycarbonate-polyorganosiloxane copolymer (A) to the aromatic polycarbonate-based resin (B) is typically from 0.1/99. 9 to 99. 9/0.1, preferably from 1/99 to 99/1, more preferably from 2/98 to 50/50, still more preferably from 5/95 to 20/80.
  • the domain (d-1) containing the polyorganosiloxane block (A-2) is present in at least the matrix containing the aromatic polycarbonate-based resin (B) as a main component, and the domain (d-2) containing at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1) is further present inside the domain (d-1) .
  • the one domain (d-2) may be present inside the one domain (d-1), or the two or more domains (d-2) may be present inside the one domain (d-1).
  • the polycarbonate-based resin composition of the present invention necessarily has a domain (d) in which the at least one domain (d-2) is present inside the domain (d-1).
  • the matrix in the polycarbonate-based resin composition is mainly formed of at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1) as long as the ratio of the polyorganosiloxane block (A-2) to the total of the polycarbonate-polyorganosiloxane copolymer (A) and the aromatic polycarbonate-based resin (B) is not more than 50 mass%.
  • the domain (d-1) containing the polyorganosiloxane block (A-2) is preferably mainly formed of the polyorganosiloxane block (A-2) .
  • the domain (d-2) containing at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1) is preferably mainly formed of at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1), and may be mainly formed of the block derived from the aromatic polycarbonate-based resin (B) or the polycarbonate block (A-1), or may be mainly formed of both the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1).
  • Which block a detected domain is mainly formed of is judged from the contrast of an image obtained by observation with a scanning probe microscope (SPM) .
  • SPM scanning probe microscope
  • a domain showing contrast comparable to that of the matrix among the detected domains is judged to be mainly formed of at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1).
  • a domain showing so dark contrast as to be clearly distinguished from the matrix among the detected domains is judged to be mainly formed of the polyorganosiloxane block (A-2).
  • the domain (d-1) containing the polyorganosiloxane block (A-2) is substantially formed of the polyorganosiloxane block (A-2).
  • the domain (d-2) containing at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1) is substantially formed of at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1), and may be substantially formed of the block derived from the aromatic polycarbonate-based resin (B) or the polycarbonate block (A-1), or may be substantially formed of both the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1).
  • the polycarbonate-based resin composition of the present invention has a core-shell structure having the domain (d-1) forming a shell in the matrix and the one domain (d-2) forming a core therein.
  • the composition may have a structure in which the two or more domains (d-2) each having a spherical shape or a cylindrical shape are incorporated inside the one domain (d-1), or a microphase-separated structure, such as a gyroid structure, a lamellar structure, or a salami structure.
  • the ratio of the number of the domains (d) each having the domain (d-2) inside the domain (d-1) to the total number of the domains (d) and the domains (d') each formed only of the domain (d-1) in the polycarbonate-based resin composition is preferably from 2% to 100%.
  • the ratio of the number of the domains (d) is more preferably from 2% to 50%, still more preferably from 5% to 45%, particularly preferably from 15% to 30%.
  • the numbers of the respective domains (d) and (d') were visually measured with a SPM.
  • the average cross-section area of all domains corresponding to the total of the domains (d) and the domains (d') is preferably 200 nm 2 or more. When the average cross-section area of all the domains is 200 nm 2 or more, more excellent impact resistance can be obtained. In addition, the average cross-section area of all the domains corresponding to the total of the domains (d) and the domains (d') is preferably 20,000 nm 2 or less. When the average cross-section area of all the domains is 20,000 nm 2 or less, more excellent impact resistance can be obtained.
  • the average cross-section area of all the domains corresponding to the total of the domains (d) and the domains (d') is more preferably from 300 nm 2 to 5,000 nm 2 , still more preferably from 500 nm 2 to 4,000 nm 2 , particularly preferably from 1,000 nm 2 to 4,000 nm 2 .
  • the average cross-section area of the respective domains (d) and (d') was calculated by observing the domains with a SPM and processing the resultant image with image analysis software (SPIP) .
  • SPIP image analysis software
  • an average cross-section area in the case where the domains (d) and (d') each had an opening portion at the time of the observation with the SPM was calculated as described below. In the case where one domain had one opening portion as illustrated in Fig.
  • the mean inter-particle distance of all the domains corresponding to the total of the domains (d) and the domains (d') in the polycarbonate-based resin composition of the present invention is preferably 500 nm or less.
  • the mean inter-particle distance of all the domains represents the frequency of presence of all the domains in the matrix. When the mean inter-particle distance of all the domains is 500 nm or less, more excellent impact resistance can be obtained. When the mean inter-particle distance of all the domains is 50 nm or more, more excellent impact resistance can be obtained.
  • the mean inter-particle distance of all the domains is more preferably from 70 nm to 350 nm, still more preferably from 110 nm to 300 nm, particularly preferably from 180 nm to 200 nm.
  • the mean inter-particle distance of all the domains was calculated by observing the particles with a SPM and processing the resultant image with image analysis software (SPIP).
  • the polycarbonate-based resin composition of the present invention has impact resistance more excellent than that of a polycarbonate-based resin composition having a comparable polyorganosiloxane chain length or containing a comparable polyorganosiloxane block amount is unclear, a possible reason is as described below.
  • the domain (d) of the polycarbonate-based resin composition according to the present invention the domain (d-2) containing at least one selected from the block derived from the aromatic polycarbonate-based resin (B) and the polycarbonate block (A-1) is present inside the domain (d-1) containing the polyorganosiloxane block (A-2).
  • the domain (d) including the domain (d-2) is increased in size as compared to the domain (d') formed only of the domain (d-1), and hence its size becomes larger than the size of the domain (d').
  • the size of the domain (d) present in the matrix entirely increases, and hence the propagation of a stress wave at the time of the application of an impact load to the polycarbonate-based resin composition may be further suppressed.
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin composition of the present invention is preferably from 0.1 mass% to 10 mass%, more preferably from 0.5 mass% to 8.0 mass%, still more preferably from 1.0 mass% to 5.0 mass%, particularly preferably from 2.0 mass% to 4.0 mass%.
  • an excellent impact-resisting characteristic can be obtained.
  • the viscosity-average molecular weight (Mv) of the polycarbonate-based resin composition of the present invention can be appropriately adjusted with a molecular weight modifier (terminal stopper) or the like so as to be a target molecular weight in accordance with applications and products in which the composition is used.
  • the viscosity-average molecular weight of the polycarbonate-based resin composition is preferably from 9,000 to 50,000, more preferably from 12,000 to 30,000, still more preferably from 14,000 to 23,000, particularly preferably from 16,000 to 20,000.
  • the viscosity-average molecular weight is 9,000 or more, a sufficient strength of a molded article of the composition can be obtained.
  • injection molding or extrusion molding can be performed at the temperature at which the heat deterioration of the composition does not occur.
  • the domain (d-1) contains the following polyorganosiloxane block (A-2) of the polycarbonate-polyorganosiloxane copolymer (A), and is preferably formed of the polyorganosiloxane block (A-2).
  • the polycarbonate-polyorganosiloxane copolymer (A) contains the polycarbonate block (A-1) formed of a repeating unit represented by the following general formula (I) and the polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II):
  • R 1 to R 4 , X, and a and b are as described above.
  • examples of the halogen atom that R 1 and R 2 each independently represent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups (the term "various" means that a linear group and all kinds of branched groups are included, and in this description, the same applies hereinafter), various pentyl groups, and various hexyl groups.
  • alkoxy group examples include alkoxy groups having the above-mentioned alkyl groups as alkyl group moieties.
  • Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. Among them, an alkylene group having 1 to 5 carbon atoms is preferred.
  • Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group.
  • Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group. Among them, a cycloalkylene group having 5 to 10 carbon atoms is preferred.
  • Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2 -adamantylidene group. Among them, a cycloalkylidene group having 5 to 10 carbon atoms is preferred, and a cycloalkylidene group having 5 to 8 carbon atoms is more preferred.
  • Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups each having 6 to 14 ring-forming carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group, and examples of the alkylene group include the above-mentioned alkylene groups.
  • Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups each having 6 to 14 ring-forming carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group, and examples of the alkylidene group include the above-mentioned alkylidene groups.
  • a and beach independently represent an integer of from 0 to 4, preferably from 0 to 2, more preferably 0 or 1.
  • a repeating unit in which a and b each represent 0, and X represents a single bond or an alkylene group having 1 to 8 carbon atoms, or a repeating unit in which a and b each represent 0, and X represents an alkylene group having 3 carbon atoms, in particular an isopropylidene group is suitable.
  • examples of the halogen atom represented by R 3 or R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • examples of the alkyl group represented by R 3 or R 4 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups.
  • Examples of the alkoxy group represented by R 3 or R 4 include alkoxy groups having the above-mentioned alkyl groups as alkyl group moieties.
  • Examples of the aryl group represented by R 3 or R 4 include a phenyl group and a naphthyl group.
  • R 3 and R 4 each preferably represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and each more preferably represent a methyl group.
  • the polyorganosiloxane block (A-2) containing the repeating unit represented by the general formula (II) preferably has a unit represented by any one of the following general formulae (II-I) to (II-III): wherein R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R 3 , R 4 , R 5 or R 6 may be identical to or different from each other, Y represents -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O-, or -R 7 O-R 10 -O-, and a plurality of Y may be identical to or different from each other, the R 7 represents
  • Examples of the halogen atom that R 3 to R 6 each independently represent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group that R 3 to R 6 each independently represent include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups.
  • Examples of the alkoxy group that R 3 to R 6 each independently represent include alkoxy groups having the above-mentioned alkyl groups as alkyl group moieties.
  • Examples of the aryl group that R 3 to R 6 each independently represent include a phenyl group and a naphthyl group.
  • R 3 to R 6 each preferably represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • R 3 to R 6 in the general formula (II-I), the general formula (II-II), and/or the general formula (II-III) each preferably represent a methyl group.
  • the linear or branched alkylene group represented by R 7 in -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O-, or -R 7 O-R 10 -O- represented by Y is, for example, an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms
  • the cyclic alkylene group represented by R 7 is, for example, a cycloalkylene group having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.
  • the aryl-substituted alkylene group represented by R 7 may have a substituent, such as an alkoxy group or an alkyl group, on its aromatic ring, and a specific structure thereof may be, for example, a structure represented by the following general formula (i) or (ii).
  • the alkylene group is bonded to Si.
  • c represents a positive integer and typically represents an integer of from 1 to 6.
  • the diarylene group represented by any one of R 7 , R 9 and R 10 refers to a group in which two arylene groups are linked to each other directly or through a divalent organic group, and is specifically a group having a structure represented by -Ar 1 -W-Ar 2 .
  • Ar 1 and Ar 2 each represent an arylene group
  • W represents a single bond or a divalent organic group.
  • Examples of the divalent organic group represented by W include an isopropylidene group, a methylene group, a dimethylene group, and a trimethylene group.
  • Examples of the arylene group represented by any one of R 7 , Ar 1 , and Ar 2 include arylene groups each having 6 to 14 ring-forming carbon atoms, such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. Those arylene groups may each have an arbitrary substituent, such as an alkoxy group or an alkyl group.
  • the alkyl group represented by R 8 is a linear or branched group having 1 to 8, preferably 1 to 5 carbon atoms.
  • the alkenyl group represented by R 8 is, for example, a linear or branched group having 2 to 8, preferably 2 to 5 carbon atoms.
  • the aryl group represented by R 8 is, for example, a phenyl group or a naphthyl group.
  • the aralkyl group represented by R 8 is, for example, a phenylmethyl group or a phenylethyl group.
  • the linear, branched, or cyclic alkylene group represented by R 10 is the same as that represented by R 7 .
  • Y preferably represents -R 7 O-.
  • R 7 preferably represents an aryl-substituted alkylene group, in particular a residue of a phenol-based compound having an alkyl group, and more preferably represents an organic residue derived from allylphenol or an organic residue derived from eugenol.
  • ⁇ represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid, and examples thereof include divalent groups represented by the following general formulae (iii) to (vii) .
  • the average chain length n of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably from 30 to 500, more preferably from 35 to 400, still more preferably from 40 to 400, still further more preferably from 50 to 300, particularly preferably from 55 to 120.
  • the average chain length is calculated by nuclear magnetic resonance (NMR) measurement. When the average chain length n falls within the range of from 30 to 500, more excellent impact resistance can be obtained.
  • the average chain length n of the polyorganosiloxane block (A- 2) also preferably falls within the range of from 55 to 500.
  • the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably from 5 mass% to 70 mass%, more preferably from 6 mass% to 50 mass%, still more preferably from 10 mass% to 45 mass%, particularly preferably from 21 mass% to 40 mass%.
  • the amount of the polyorganosiloxane block in the PC-POS copolymer (A) falls within the range, more excellent impact resistance can be obtained.
  • the viscosity-average molecular weight (Mv) of the PC-POS copolymer (A) can be appropriately adjusted with a molecular weight modifier (terminal stopper) or the like so as to be a target molecular weight in accordance with applications and products in which the copolymer is used.
  • the viscosity-average molecular weight is preferably from 9,000 to 50,000, more preferably from 12,000 to 30,000, still more preferably from 14,000 to 23,000, particularly preferably from 16,000 to 22,000, most preferably from 16,000 to 20,000.
  • the viscosity-average molecular weight is 9,000 or more, a sufficient strength of a molded article of the copolymer can be obtained.
  • injection molding or extrusion molding can be performed at the temperature at which the heat deterioration of the copolymer does not occur.
  • the polycarbonate-polyorganosiloxane copolymer (A) can be produced by a known production method, such as an interfacial polymerization method (phosgene method), a pyridine method, or an ester exchange method.
  • a step of separating an organic phase containing the PC-POS copolymer (A) and an aqueous phase containing an unreacted product, a catalyst residue, or the like becomes easier, and hence the separation of the organic phase containing the PC-POS copolymer (A) and the aqueous phase in each washing step based on alkali washing, acid washing, or pure water washing becomes easier. Accordingly, the PC-POS copolymer (A) is efficiently obtained.
  • a method of producing the PC-POS copolymer (A) reference can be made to, for example, a method described in JP 2010-241943 A .
  • the PC-POS copolymer (A) can be produced by: dissolving a polycarbonate oligomer produced in advance to be described later and a polyorganosiloxane in a water-insoluble organic solvent (e.g., methylene chloride); adding a solution of a dihydric phenol-based compound (e.g., bisphenol A) in an aqueous alkaline compound (e.g., aqueous sodium hydroxide) to the solution; and subjecting the mixture to an interfacial polycondensation reaction through the use of a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., trimethylbenzylammonium chloride) as a polymerization catalyst in the presence of a terminal stopper (a monohydric phenol, such asp- t-butylphenol) .
  • a terminal stopper a monohydric phenol, such asp- t-buty
  • the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate-based resin composition of the present invention is produced by, for example, causing the polycarbonate oligomer and a polyorganosiloxane raw material to react with each other in an organic solvent, and then causing the resultant to react with the dihydric phenol, the solid matter weight (g/L) of the polycarbonate oligomer in 1 L of a mixed solution of the organic solvent and the polycarbonate oligomer falls within the range of preferably from 80 g/L to 200 g/L, more preferably from 90 g/L to 180 g/L, still more preferably from 100 g/L to 170 g/L.
  • a polyorganosiloxane represented by the following general formula (1), general formula (2), and/or general formula (3) can be used as the polyorganosiloxane serving as a raw material: wherein, R 3 to R 6 , Y, ⁇ , n-1, p and q are as described above, and specific examples and preferred examples thereof are also the same as those described above, and
  • Z represents a hydrogen atom or a halogen atom, and a plurality of Z may be identical to or different from each other.
  • Examples of the polyorganosiloxane represented by the general formula (1) include compounds each represented by any one of the following general formulae (1-1) to (1-11):
  • R 3 to R 6 , n, and R 8 are as defined above, and preferred examples thereof are also the same as those described above, and c represents a positive integer and typically represents an integer of from 1 to 6.
  • a phenol-modified polyorganosiloxane represented by the general formula (1-1) is preferred from the viewpoint of its ease of polymerization.
  • an ⁇ , ⁇ -bis[3-( o -hydroxyphenyl)propyl]polydimethylsiloxane, which is one of compound represented by the general formula (1-2), or an ⁇ , ⁇ -bis[3-(4-hydroxy-3-methoxyphenyl)propyl]polydimethylsiloxa ne, which is one of compound represented by the general formula (1-3), is preferred from the viewpoint of its ease of availability.
  • a compound having a structure represented by the following general formula (4) may be used as a polyorganosiloxane raw material: wherein R 3 and R 4 are identical to those described above.
  • the average chain length of the polyorganosiloxane block represented by the general formula (4) is (r ⁇ m), and the range of the (r ⁇ m) is the same as that of the n.
  • the polyorganosiloxane block (A-2) preferably has a unit represented by the following general formula (II-IV): wherein R 3 , R 4 , r, and m are as described above.
  • a method of producing the polyorganosiloxane is not particularly limited. According to, for example, a method described in JP 11-217390 A , a crude polyorganosiloxane can be obtained by: causing cyclotrisiloxane and disiloxane to react with each other in the presence of an acid catalyst to synthesize ⁇ , ⁇ -dihydrogen organopentasiloxane; and then subjecting the ⁇ , ⁇ -dihydrogen organopentasiloxane to an addition reaction with, for example, a phenolic compound (e.g., 2-allylphenol, 4-allylphenol, eugenol, or 2-propenylphenol) in the presence of a catalyst for a hydrosilylation reaction.
  • a phenolic compound e.g., 2-allylphenol, 4-allylphenol, eugenol, or 2-propenylphenol
  • the crude polyorganosiloxane can be obtained by: causing octamethylcyclotetrasiloxane and tetramethyldisiloxane to react with each other in the presence of sulfuric acid (acid catalyst); and subjecting the resultant ⁇ , ⁇ -dihydrogen organopolysiloxane to an addition reaction with the phenolic compound or the like in the presence of the catalyst for a hydrosilylation reaction in the same manner as that described above.
  • the ⁇ , ⁇ -dihydrogen organopolysiloxane may be used after its chain length n has been appropriately adjusted in accordance with its polymerization conditions, or a commercial ⁇ , ⁇ -dihydrogen organopolysiloxane may be used.
  • Examples of the catalyst for a hydrosilylation reaction include transition metal-based catalysts. Among them, a platinum-based catalyst is preferably used in terms of a reaction rate and selectivity. Specific examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, a complex of platinum and a vinyl group-containing siloxane, platinum-supported silica, and platinum-supported activated carbon.
  • the crude polyorganosiloxane is preferably brought into contact with an adsorbent to cause the adsorbent to adsorb and remove a transition metal derived from a transition metal-based catalyst in the crude polyorganosiloxane, the catalyst having been used as the catalyst for a hydrosilylation reaction.
  • An adsorbent having an average pore diameter of, for example, 1,000 ⁇ or less can be used as the adsorbent.
  • the average pore diameter of the adsorbent is preferably 500 ⁇ or less, more preferably 200 ⁇ or less, still more preferably 150 ⁇ or less, still further more preferably 100 ⁇ or less.
  • the adsorbent is preferably a porous adsorbent.
  • the adsorbent is not particularly limited as long as the adsorbent has the above-mentioned average pore diameter, for example, activated clay, acid clay, activated carbon, synthetic zeolite, natural zeolite, activated alumina, silica, a silica-magnesia-based adsorbent, diatomaceous earth, or cellulose can be used, and at least one selected from the group consisting of activated clay, acid clay, activated carbon, synthetic zeolite, natural zeolite, activated alumina, silica, and a silica-magnesia-based adsorbent is preferred.
  • the adsorbent After the adsorbent has been caused to adsorb the transition metal in the crude polyorganosiloxane, the adsorbent can be separated from the polyorganosiloxane by arbitrary separating means.
  • the means for separating the adsorbent from the polyorganosiloxane include a filter and centrifugal separation.
  • a filter such as a membrane filter, a sintered metal filter, or a glass fiber filter, can be used.
  • a membrane filter is particularly preferably used.
  • the average particle diameter of the adsorbent is typically from 1 ⁇ m to 4 mm, preferably from 1 ⁇ m to 100 ⁇ m from the viewpoint that the adsorbent is separated from the polyorganosiloxane after the adsorption of the transition metal.
  • the porous adsorbent can be used in an amount in the range of preferably from 1 part by mass to 30 parts by mass, more preferably from 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the crude polyorganosiloxane.
  • the polyorganosiloxane When the crude polyorganosiloxane to be treated has so high a molecular weight that the polyorganosiloxane is not in a liquid state, the polyorganosiloxane may be heated to such a temperature as to be in a liquid state at the time of the performance of the adsorption with the adsorbent and the separation of the adsorbent. Alternatively, the adsorption and the separation may be performed after the polyorganosiloxane has been dissolved in a solvent, such as methylene chloride or hexane.
  • a solvent such as methylene chloride or hexane.
  • a polyorganosiloxane having a desired molecular weight distribution is obtained by regulating its molecular weight distribution through, for example, the blending of a plurality of polyorganosiloxanes.
  • a crude polyorganosiloxane having a desired molecular weight distribution can be obtained by blending a plurality of ⁇ , ⁇ -dihydrogen organopolysiloxanes and then subjecting a phenolic compound or the like to an addition reaction with the resultant in the presence of a catalyst for a hydrosilylation reaction.
  • purification such as the removal of the catalyst for a hydrosilylation reaction, may be performed after a plurality of crude polyorganosiloxanes have been blended, and a plurality of polyorganosiloxanes after the purification may be blended.
  • a molecular weight distribution can be appropriately adjusted depending on a polymerization condition at the time of the production of a polyorganosiloxane.
  • a desired molecular weight distribution can be obtained by fractionating only part of existing polyorganosiloxanes through means such as various kinds of separation.
  • the polycarbonate oligomer can be produced by a reaction between a dihydric phenol and a carbonate precursor, such as phosgene or triphosgene, in an organic solvent, such as methylene chloride, chlorobenzene, or chloroform.
  • a carbonate precursor such as phosgene or triphosgene
  • organic solvent such as methylene chloride, chlorobenzene, or chloroform.
  • the oligomer can be produced by a reaction between the dihydric phenol and a carbonate precursor, such as diphenyl carbonate.
  • a dihydric phenol represented by the following general formula (viii) is preferably used as the dihydric phenol: wherein R 1 , R 2 , a, b, and X are as described above.
  • Examples of the dihydric phenol represented by the general formula (viii) include: bis (hydroxyphenyl) alkane dihydric phenols, such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane; 4,4'-dihydroxydiphenyl; bis(4-hydroxyphenyl)cycloalkanes; bis(4-hydroxyphenyl) oxide; bis(4-hydroxyphenyl) sulfide; bis(4-hydroxyphenyl) sulfone; bis(4-hydroxyphenyl) sulfoxide; and bis(4-hydroxyphenyl) ketone.
  • Those dihydric phenols may be used alone or as a mixture thereof.
  • bis(hydroxyphenyl)alkane dihydric phenols are preferred, and bisphenol A is more preferred.
  • dihydric phenol examples include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxydiphenyls, dihydroxydiarylfluorenes, and dihydroxydiaryl adamantanes .
  • Those dihydric phenols may be used alone or as a mixture thereof.
  • bis(hydroxyaryl)alkanes examples include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3- t -butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane
  • Examples of the bis(hydroxyaryl)cycloalkanes include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, and 1,1-bis(4-hydroxyphenyl)cyclododecane.
  • Examples of the dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.
  • dihydroxydiaryl sulfides examples include 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide.
  • dihydroxydiaryl sulfoxides examples include 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide.
  • dihydroxydiaryl sulfones examples include 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.
  • dihydroxydiphenyls is 4,4'-dihydroxydiphenyl.
  • dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl) fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.
  • dihydroxydiaryladamantanes include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.
  • dihydric phenols examples include 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, and 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane.
  • a terminal stopper (molecular weight modifier) may be used.
  • the terminal stopper include monohydric phenols, such as phenol, p -cresol, p - tert -butylphenol, p - tert -octylphenol, p -cumylphenol, p -nonylphenol, m -pentadecylphenol, and p-tert -amylphenol.
  • monohydric phenols such as phenol, p -cresol, p - tert -butylphenol, p - tert -octylphenol, p -cumylphenol, p -nonylphenol, m -pentadecylphenol, and p-tert -amylphenol.
  • Those monohydric phenols may be used alone or in combination thereof.
  • the PC-POS copolymer (A) can be obtained by appropriately leaving the resultant at rest to separate the resultant into an aqueous phase and an organic solvent phase [separating step], washing the organic solvent phase (preferably washing the phase with a basic aqueous solution, an acidic aqueous solution and water, in order) [washing step], concentrating the resultant organic phase [concentrating step], and drying the concentrated phase [drying step].
  • the aromatic polycarbonate-based resin (B) except the polycarbonate-polyorganosiloxane copolymer (A) forms the matrix moiety of the polycarbonate-based resin composition of the present invention, and is incorporated into the domain (d-2).
  • the aromatic polycarbonate-based resin (B) contains a polycarbonate block comprising, in a main chain thereof, a repeating unit represented by the following general formula (III).
  • the polycarbonate-based resin is not particularly limited, and various known polycarbonate-based resins can be used.
  • R 9 and R 10 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms
  • X' represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO 2 -, -O-, or -CO-, and d and e each independently represent an integer of from 0 to 4.
  • R 9 and R 10 include the same examples as those of R 1 and R 2 , and preferred examples thereof are also the same as those of R 1 and R 2 .
  • R 9 and R 10 each more preferably represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • Specific examples of X' include the same examples as those of X, and preferred examples thereof are also the same as those of X.
  • d and e each independently represent preferably from 0 to 2, more preferably 0 or 1.
  • a resin obtained by a conventional production method for a polycarbonate can be used as the aromatic polycarbonate-based resin (B) .
  • the conventional method include: an interfacial polymerization method involving causing the dihydric phenol-based compound and phosgene to react with each other in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, adding a polymerization catalyst, such as a tertiary amine or a quaternary ammonium salt, to the resultant, and polymerizing the mixture; and a pyridine method involving dissolving the dihydric phenol-based compound in pyridine or a mixed solution of pyridine and an inert solvent, and introducing phosgene to the solution to directly produce the resin.
  • a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt
  • a molecular weight modifier (terminal stopper), a branching agent, or the like is used as required in the reaction.
  • the dihydric phenol -based compound is, for example, a compound represented by the following general formula (III'): wherein R 9 , R 10 , X', d, and e are as defined above, and preferred examples thereof are also the same as those described above.
  • dihydric phenol-based compound may include those described above in the method of producing the polycarbonate-polyorganosiloxane copolymer (A), and preferred examples thereof are also the same as those described above. Among them, bis(hydroxyphenyl)alkane-based dihydric phenols are preferred, and bisphenol A is more preferred.
  • the aromatic polycarbonate-based resins may be used alone or in combination thereof.
  • the aromatic polycarbonate resin (B) may have a structure free of such a polyorganosiloxane block as represented by the formula (II) unlike the polycarbonate-polyorganosiloxane copolymer (A).
  • the aromatic polycarbonate-based resin (B) may be a homopolycarbonate resin.
  • any other additive can be incorporated into the polycarbonate-based resin composition of the present invention to the extent that the effects of the present invention are not impaired.
  • the other additive may include a flame retardant, a flame retardant aid, a release agent, a reinforcing material, a filler, an elastomer for an impact resistance improvement, a dye, and a pigment.
  • the polycarbonate-based resin composition of the present invention is obtained by: blending the above-mentioned respective components at the above-mentioned ratios and various optional components to be used as required at appropriate ratios; and kneading the components.
  • the blending and the kneading may be performed by a method involving premixing with a typically used apparatus, such as a ribbon blender or a drum tumbler, and using, for example, a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, or a Ko-kneader.
  • a heating temperature at the time of the kneading is appropriately selected from the range of from 240°C to 320°C.
  • An extruder, in particular a vented extruder is preferably used in the melt-kneading.
  • Various molded bodies can each be produced by an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, an expansion molding method, or the like using as a raw material the melt-kneadedpolycarbonate-based resin composition of the present invention or a pellet obtained through the melt-kneading.
  • the pellet obtained through the melt-kneading can be suitably used in the production of injection-molded bodies by injection molding and injection compression molding.
  • the molded article comprising the polycarbonate-based resin composition of the present invention can be suitably used as, for example: a casing for a part for electrical and electronic equipment, such as a television, a radio-cassette player, a video camera, a videotape recorder, an audio player, aDVDplayer, an air conditioner, a cellular phone, a display, a computer, a register, an electronic calculator, a copying machine, a printer, or a facsimile; or a part for an automobile and a building material.
  • a casing for a part for electrical and electronic equipment such as a television, a radio-cassette player, a video camera, a videotape recorder, an audio player, aDVDplayer, an air conditioner, a cellular phone, a display, a computer, a register, an electronic calculator, a copying machine, a printer, or a facsimile; or a part for an automobile and a building material.
  • the chain length and content of a polydimethylsiloxane were calculated by NMR measurement from the integrated value ratio of a methyl group of the polydimethylsiloxane.
  • a viscosity-average molecular weight (Mv) was calculated from the following equation (Schnell's equation) by using a limiting viscosity [n] determined through the measurement of the viscosity of a methylene chloride solution at 20°C with an Ubbelohde-type viscometer.
  • ⁇ 1.23 ⁇ 10 ⁇ 5 ⁇ Mv 0.83
  • the number of all domains to be evaluated was automatically calculated with the SPIP, and the number of the domains (d) was visually counted.
  • the cross-section areas of the respective domains were automatically calculated by subjecting the domains to image processing with the SPIP, and their average was calculated.
  • BPA bisphenol A
  • aqueous sodium hydroxide was prepared.
  • the solution of BPA in aqueous sodium hydroxide, methylene chloride, and phosgene were continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 L/hr, 15 L/hr, and 4.0 kg/hr, respectively.
  • the tubular reactor had a jacket portion and the temperature of the reaction liquid was kept at 40°C or less by passing cooling water through the jacket.
  • the reaction liquid that had exited the tubular reactor was continuously introduced into a baffled vessel type reactor provided with a sweptback blade and having an internal volume of 40 L.
  • the solution of BPA in aqueous sodium hydroxide, 25 mass% aqueous sodium hydroxide, water, and a 1 mass% aqueous solution of triethylamine were further added to the reactor at flow rates of 2.8 L/hr, 0.07 L/hr, 17 L/hr, and 0.64 L/hr, respectively, to perform a reaction.
  • An aqueous phase was separated and removed by continuously taking out the reaction liquid overflowing the vessel type reactor and leaving the reaction liquid at rest. Then, a methylene chloride phase was collected.
  • the polycarbonate oligomer thus obtained had a concentration of 330 g/L and a chloroformate group concentration of 0.71 mol/L.
  • PDMS polydimethylsiloxane
  • a solution of p -t-butylphenol (PTBP) in methylene chloride obtained by dissolving (viii) g of PTBP in (ix) L of methylene chloride (MC)
  • a solution of BPA in aqueous sodium hydroxide obtained by dissolving (xiii) gof BPA in an aqueous solution obtained by dissolving (x) g of NaOH and (xi) g of sodium dithionite (Na 2 S 2 O 4 ) in (xii) L of water) were added to the polymerization liquid, and the mixture was subj ected to a polymerization reaction for 40 minutes.
  • a solution of the PC-POS in methylene chloride thus obtained was sequentially washed with 0.03 mol/L aqueous NaOH and 0.2 mol/L hydrochloric acid in amounts of 15 vol% each with respect to the solution. Next, the solution was repeatedly washed with pure water until an electric conductivity in an aqueous phase after the washing became 0.01 ⁇ S/m or less.
  • PC-POS copolymers A1 to A17 obtained in Production Examples 1 to 17, and other respective components were mixed at blending ratios shown in Table 2-1 to Table 2-3, and the mixture was supplied to a vented twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-35B) and melt-kneaded at a screw revolution number of 150 rpm, an ejection amount of 20 kg/hr, and a resin temperature of from 295°C to 300°C to provide an evaluation pellet sample.
  • the measurement of a PDMS content, an Mv, a MFR, a Q value, and impact resistance, and image observation and image analysis with a SPM were performed by using the evaluation pellet sample.
  • Typical images (the images each correspond to a 1-micrometer square) of the results of the observation of the polycarbonate resin compositions obtained in Examples 1 to 8 and Comparative Example 4 with the SPM are shown in Figs. 1 to 9 .
  • the amount (g/10 min) of a molten resin flowing out of a die having a diameter of 2 mm and a length of 8 mm was measured by using the above-mentioned pellet in conformity with JIS K 7210 at 300°C under a load of 1.2 kg.
  • the amount (mL/sec) of a molten resin flowing out of a nozzle having a diameter of 1 mm and a length of 10 mm was measured by using the above-mentioned pellet and a Koka flow tester in conformity with JIS K 7210 at 280°C under a pressure of 15.9 MPa.
  • a Q value represents an outflow amount per unit time, and a higher numerical value therefor means that the fluidity of the resin is better.
  • the above-mentioned resultant pellet was dried at 120°C for 8 hours. After that, the dried product was subjected to injection molding with an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., NEX110, screw diameter: 36 mm ⁇ ) at a cylinder temperature of 280°C and a mold temperature of 80°C to produce an IZOD test piece (measuring 63 mm by 13 mm by 3.2 mm). Notched Izod impact strengths at -40°C and, in some cases, 23°C were measured by using a test piece obtained by making a notch in the test piece through post-processing in conformity with the ASTM standard D-256.
  • an injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., NEX110, screw diameter: 36 mm ⁇
  • the polycarbonate resin obtained in the present invention can be suitably used as a casing and the like for a part for electrical and electronic equipment, and a part and the like for an automobile and a building material because the resin is excellent in impact resistance.

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Claims (21)

  1. Composition de résine à base de polycarbonate, comprenant :
    un copolymère de polycarbonate-polyorganosiloxane (A) contenant une séquence de polycarbonate (A-1) comprenant un motif répétitif représenté par la formule générale (I) suivante et une séquence de polyorganosiloxane (A-2) comprenant un motif répétitif représenté par la formule générale (II) suivante ; et
    une résine à base de polycarbonate aromatique (B) à l'exception du copolymère de polycarbonate-polyorganosiloxane (A),
    dans laquelle la composition de résine à base de polycarbonate présente une structure dans laquelle un domaine (d-1) contenant la séquence de polyorganosiloxane (A-2) est présent dans une matrice contenant la résine à base de polycarbonate aromatique (B) en tant que composant principal, et un domaine (d-2) contenant au moins l'une sélectionnée parmi une séquence dérivée de la résine à base de polycarbonate aromatique (B) et la séquence de polycarbonate (A-1) est présent à l'intérieur du domaine (d-1) :
    Figure imgb0058
    Figure imgb0059
     dans laquelle R1 et R2 représentent chacun indépendamment un atome d'halogène, un groupe alkyle présentant 1 à 6 atomes de carbone, ou un groupe alcoxy présentant 1 à 6 atomes de carbone, X représente une liaison simple, un groupe alkylène présentant 1 à 8 atomes de carbone, un groupe alkylidène présentant 2 à 8 atomes de carbone, un groupe cycloalkylène présentant 5 à 15 atomes de carbone, un groupe cycloalkylidène présentant 5 à 15 atomes de carbone, un groupe fluorènediyle, un groupe arylalkylène présentant 7 à 15 atomes de carbone, un groupe arylalkylidène présentant 7 à 15 atomes de carbone, -S-, -SO-, -SO2-, -O- ou -CO-, R3 et R4 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, un groupe alkyle présentant 1 à 6 atomes de carbone, un groupe alcoxy présentant 1 à 6 atomes de carbone ou un groupe aryle présentant 6 à 12 atomes de carbone, et a et b représentent chacun indépendamment un nombre entier allant de 0 à 4.
  2. Composition de résine à base de polycarbonate selon la revendication 1, dans laquelle un rapport en masse « (A)/(B) » entre le copolymère de polycarbonate-polyorganosiloxane (A) et la résine à base de polycarbonate aromatique (B) est de 0,1/99,9 à 99,9/0,1.
  3. Composition de résine à base de polycarbonate selon la revendication 1 ou 2, dans laquelle la résine à base de polycarbonate aromatique (B) contient une séquence de polycarbonate comprenant, dans une chaîne principale de celle-ci, un motif répétitif représentée par la formule générale (III) suivante :
    Figure imgb0060
     dans laquelle R9 et R10 représentent chacun indépendamment un atome d'halogène, un groupe alkyle présentant 1 à 6 atomes de carbone ou un groupe alcoxy présentant 1 à 6 atomes de carbone , X' représente une liaison simple, un groupe alkylène présentant 1 à 8 atomes de carbone, un groupe alkylidène présentant 2 à 8 atomes de carbone, un groupe cycloalkylène présentant 5 à 15 atomes de carbone, un groupe cycloalkylidène présentant 5 à 15 atomes de carbone, -S-, -SO-, -SO2-, -O- ou -CO-, et d et e représentent chacun indépendamment un nombre entier allant de 0 à 4.
  4. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 3, dans laquelle le domaine (d-1) est principalement formé de la séquence de polyorganosiloxane (A-2).
  5. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 4, dans laquelle le domaine (d-2) est principalement formé d'au moins l'une sélectionnée parmi la séquence dérivée de la résine à base de polycarbonate aromatique (B) et la séquence de polycarbonate (A-1).
  6. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 5, dans laquelle seulement un domaine (d-2) est présent à l'intérieur du domaine (d-1).
  7. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 5, dans laquelle deux ou plus de deux domaines (d-2) sont présents à l'intérieur du domaine (d-1).
  8. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 7, dans laquelle un rapport entre un nombre de domaines (d) dans chacun desquels le domaine (d-2) est présent à l'intérieur du domaine (d-1) et un nombre total des domaines (d) et des domaines (d') formés chacun uniquement du domaine (d-1) est de 2 % à 100 %.
  9. Composition de résine à base de polycarbonate selon la revendication 8, dans laquelle une surface moyenne en coupe transversale de tous les domaines correspondant à un total des domaines (d) et des domaines (d') est de 200 nm2 ou plus.
  10. Composition de résine à base de polycarbonate selon la revendication 8 ou 9, dans laquelle une surface moyenne en coupe transversale de tous les domaines correspondant à un total des domaines (d) et des domaines (d') est de 20 000 nm2 ou moins.
  11. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 8 à 10, dans laquelle une distance inter-particules moyenne de tous les domaines correspondant à un total des domaines (d) et des domaines (d') est de 500 nm ou moins.
  12. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 8 à 11, dans laquelle une distance inter-particules moyenne de tous les domaines correspondant à un total des domaines (d) et des domaines (d') est de 50 nm ou plus.
  13. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 12, dans laquelle la séquence de polyorganosiloxane (A-2) présente une longueur moyenne de chaîne allant de 30 à 500.
  14. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 13, dans laquelle la séquence de polyorganosiloxane (A-2) présente une longueur moyenne de chaîne allant de 55 à 500.
  15. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 14, dans laquelle une teneur de la séquence de polyorganosiloxane (A-2) dans le copolymère de polycarbonate-polyorganosiloxane (A) est de 5 % en masse à 70 % en masse.
  16. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 15, dans laquelle une teneur de la séquence de polyorganosiloxane (A-2) dans la composition de résine à base de polycarbonate est de 0,1 % en masse à 10 % en masse.
  17. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 16, dans laquelle le copolymère de polycarbonate-polyorganosiloxane (A) présente un poids moléculaire moyen en viscosité (Mv) de 9 000 à 50 000, dans laquelle le poids moléculaire moyen en viscosité (Mv) est déterminé selon le procédé divulgué dans le mémoire.
  18. Composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 17, dans laquelle la composition de résine à base de polycarbonate présente un poids moléculaire moyen en viscosité (Mv) de 9 000 à 50 000, dans laquelle le poids moléculaire moyen en viscosité (Mv) est déterminé selon le procédé divulgué dans le mémoire.
  19. Article moulé, qui est obtenu par le moulage de la composition de résine à base de polycarbonate selon l'une quelconque des revendications 1 à 18.
  20. Article moulé selon la revendication 19, dans lequel l'article moulé comprend un boîtier pour un équipement électrique et électronique.
  21. Article moulé selon la revendication 19, dans lequel l'article moulé comprend une pièce pour une automobile et un matériau de construction.
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CN107922727A (zh) 2018-04-17
EP3342824A1 (fr) 2018-07-04
KR102543776B1 (ko) 2023-06-14
WO2017034039A1 (fr) 2017-03-02
JPWO2017034039A1 (ja) 2018-06-14
JP2020172665A (ja) 2020-10-22
TW201714956A (zh) 2017-05-01
TWI694111B (zh) 2020-05-21
US20180251606A1 (en) 2018-09-06
JP6837976B2 (ja) 2021-03-03
EP3342824A9 (fr) 2020-01-01
EP3342824A4 (fr) 2019-04-24
CN107922727B (zh) 2021-03-26
KR20180044907A (ko) 2018-05-03
JP7040708B2 (ja) 2022-03-23
US10550229B2 (en) 2020-02-04

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